Superconducting wire with improved strain characteristics

ABSTRACT

A superconducting wire comprising a superconducting filament and a beryllium strengthened bronze matrix in which the addition of beryllium to the matrix permits a low volume matrix to exhibit reduced elastic deformation after heat treating which increases the compression of the superconducting filament on cooling and thereby improves the strain characteristics of the wire.

BACKGROUND OF THE INVENTION

The invention described herein was made or conceived in the course of,or under a contract with, the United States Department of Energy.

This application is a divisional of co-pending application Ser. No.105,439, filed Dec. 19, 1979, which application is a continuation inpart of application Ser. No. 966,709, filed Dec. 5, 1978, now abandoned.

1. Field

The invention relates to improvement in superconducting wires and, inparticular, to means for improving the strain characteristic of suchwires.

2. Prior Art

Twenty-four metallic elements and more than 1,000 alloys exhibit acharacteristic known as superconductivity. These materials, when cooledto near zero degrees Kelvin, exhibit zero resistivity. The zeroresistivity characteristic of many superconducting materials is lostwhen the material is subject to a strong magnetic field, making themunsuitable for use in the production of electromagnets.

A number of compounds, including the intermetallics niobium-tin (Nb₃ Sn)and vanadium-gallium (V₃ Ga), have been found to retain theirsuperconducting properties in the presence of magnetic fields above 200kilogauss.

Since there is no ohmic loss in a material exhibiting zero resistivity,a small gauge superconducting wire is capable of carrying high currents.Consequently, very compact, high field strength electromagnets are nowpossible. These electromagnets are considerably smaller than comparabledevices employing copper windings and water cooling.

Superconductors such as niobium-tin and vanadium-gallium are brittle andcan be easily damaged, especially when drawn into fine filamentary wireand wound for use in electromagnets. To produce a serviceable wire, thesuperconducting filament is provided with supporting material, usuallyreferred to as a matrix.

An example of a superconductor, supported by a matrix, is a matrix ofbronze surrounding a center filament of a metal such as niobium. Duringa heat treating step in the fabrication of the wire, the niobium reactswith the tin in the bronze to form a superconducting film of niobium-tinat the interface of the bronze and niobium.

The structure of a more practical wire is similar to that describedabove with the exception that multiple fine filaments of niobium, ratherthan a single filament, are embedded in the matrix.

Typically, a matrix contains a number of niobium filaments. Eachfilament is surrounded by a superconducting film of niobium-tin at theinterface between the niobium and the matrix.

When practical wires are made and are properly heat treated, virtuallyall of the niobium in the fine filaments is converted to niobium-tin;however, for the sake of brevity, the portion of niobium converted toniobium-tin will be referred to herein as the superconducting filmregardless of its thickness in each case.

In addition to the two structures described above, other practicalstructures are possible including tapes in which the superconductor iscontained within a tape matrix.

The ratio of the diameter of the matrix material to that of the filamentin a single filament wire is typically in the order of two or three toone. Although much higher ratios such as ten to one may be fabricated,the lower ratios are practical from the standpoint of cost, volume andcurrent carrying capability per unit cross section.

The bendings of the superconducting wire cause the portion of the wireat the outside of the bend to be elongated or strained. The wire canalso be strained by a tensile force occurring during the winding, oroperation of an electromagnet. This strain extends through the matrix tothe superconductor. Sufficient strain can adversely affect the currentcarrying capacity and even produce an irreversible reduction in currentcapacity.

SUMMARY

An object of the present invention is the production of superconductingwire or tape with improved strain characteristics. A second object isthe production of superconducting wire or tape in which the strainproduced by the bending of the wire or the application of a tensileforce in normal use increases the effective range of critical currentcarrying capacity.

The addition of an unusually small percentage of beryllium, ranging from0.01 to 0.2 percent by weight, to a low volume, bronze matrix for asuperconducting film adds sufficient tensile strength to the matrixduring a heat treating process to hold the superconducting filamentunder greater compression, both radial and axial, upon its formationthan has been obtained previously with a similarly sized matrix. Thehigher compression increases the strain limits and provides a morerugged wire with a higher useful current carrying capacity.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1A is a perspective view of a superconducting wire in which thematrix surrounds a single superconducting filament, said matrixcontaining a small percentage of beryllium.

FIG. 1B is a perspective view of a superconducting wire in which thematrix surrounds the superconducting filaments, said matrix containing asmall percentage of beryllium.

FIG. 2 is a graph illustrating the improvement in the straincharacteristics of a superconducting wire achieved by means of thepresent invention.

DETAILED DESCRIPTION

A superconducting wire according to the present invention is shown inFIG. 1A. A matrix 11 of bronze surrounds a center 13 of a metal such asniobium. During a heat treating step in the fabrication of the wire theniobium reacts with the tin in the bronze to form a superconducting filmof niobium-tin at the interface 12 of matrix 11 and center filament 13.

In accordance with the present invention matrix 11 contains a smallamount of beryllium, the amount being chosen so as to strengthen matrix11 sufficiently to achieve the advantages of the present invention, aswill be more fully described below, while still allowing the wire of thepresent invention to be produced by the typical fabrication process,described below, without requiring additional annealling steps. Thisamount is preferably from 0.01 to 0.2 weight percent and still morepreferably about 0.18 weight percent.

A more practical wire is shown in FIG. 1B where matrix 14 surrounds aplurality of fine filaments 15. During heat treating a plurality ofsuperconducting films are formed at interfaces 16. In accordance withthe present invention matrix 14 contains approximately the samepercentage of beryllium as matrix 11.

It is within the contemplation of this invention to also formsuperconducting wires wherein matrices 11 and 14 comprise copper-galliumalloy and filaments 13 and 15 comprise vanadium, and wheresuperconducting films of vanadium-gallium are formed at interfaces 12and 16.

The superconductive behavior of a material is lost when the currentexceeds a limit referred to as the critical current density. During themeasurement of critical current density, a superconducting wire ismaintained within a temperature range in which the wire exhibitssuperconductive behavior, while the wire is subject to a magnetic field.For example, the critical current density of niobium-tin isapproximately 1,500,000 amperes per square centimeter when thissuperconductor is subject to a magnetic field strength of 40 kilogauss.The critical current density for vanadium-gallium ranges from roughlyone-half to the same as that of niobium-tin, under the same conditions.

The critical current density is an important parameter indicating themaximum current carrying capacity of a wire. This capacity is reduced orincreased depending on the strain on the wire.

The effect of strain on the critical current density is shown in thegraph of FIG. 2. In this figure, the ordinate 21 represents the ratio ofthe critical current density to the maximum critical current density,while the abscissa 22 represents the percent strain.

Two characteristics have been plotted. The first plot 23 represents thecharacteristic of a prior art wire, while the second plot 24 representsthat of a wire produced in accordance with the present invention. Bothwires have the configuration shown in FIG. 1A. The ratio of the bronzematrix 11 diameter to that of the niobium filament 13 is 2.5 to 1 andthe tin content in the bronze matrix 11 is 11.5 percent by weight. Apreferred wire produced in accordance with the present inventionincludes 0.18 percent by weight of beryllium in the matrix 11, while theprior art matrix contains no beryllium.

The addition of this unusually small percentage of beryllium issignificant. As can be seen from the plots, the critical current densityrises, reaches a maximum, and then falls as the percent strain isincreased. The maximum for the prior art wire indicated by drawingnumeral 25 is reached at 0.6 percent strain, while the maximum for thepresent invention indicated by drawing numeral 26 is at the appreciablyhigher level of 1.0 percent strain. At 1.0 percent strain, the prior artwires current carrying capacity has dropped over 10 percent. Therepresents a loss in current carrying capacity of about 150,000 amperesper square centimeter.

As the strain is increased to 1.25 percent, the prior art wire reaches apoint of irreversible loss in current carrying capacity, indicated bythe dashed portion of the plot, while the present invention does notreach the point of irreversible loss until the strain is increased to1.75 percent. A the 1.25 percent strain level, the wire fabricated inaccordance with the present invention shows a loss in current carryingcapacity of only five percent, while the prior art wire shows a 35percent loss.

In practical applications involving a tensile force or bending of thewire, the wire produced in accordance with the present invention may bestrained to one percent or more, where it is at or near its maximumcurrent carrying capacity, whereas prior art wire, if so strained, losesfrom 10 to 35 percent of its capacity and is placed close to the pointat which irreversible loss in capacity occurs.

It is apparent that the present invention offers an advantage inproviding a maximum in current carrying capacity after having beensubject to a strain which would tend to degrade or destroy the prior artwire and the present invention can withstand greater strain beforeirreversible loss in capacity occurs.

The rise occurring in the critical current as strain is increased hasbeen noted in prior art wires: however, the reason for the rise had notbeen clearly ascertained.

It has been determined that the matrix places the superconductor incompression, both radial and axial, during a heat treatment step in thefabrication process. In this step, the temperature of the wire iselevated to about 650°-800° centigrade, and then cooled. During thecooling period, the difference in the coefficients of thermal expansionbetween the matrix and the niobium-tin causes the outer bronze matrix tocontract more than the niobium-tin, placing the niobium-tin undercompression.

Where the ratio of the matrix diameter to that of the niobium-tin is tento one, there is little plastic deformation of the bronze matrix.Essentially, the bronze contracts by the amount it would if there wereno niobium-tin in the wire; however, as the ratio of diameters isreduced below ten to one, there is an increase in the plasticdeformation of the matrix accompanied by a corresponding decrease in thecompression of the niobium-tin. The addition of the small percentage ofberyllium to the matrix adds strength at high temperatures to reduce theamount of plastic deformation of the matrix and thereby increase thecompression on the niobium-tin, especially in wire having a ratio ofmatrix volume to filament volume of about from 1-5.

Compression or tension of a superconductor, such as niobium-tin, reducesthe critical current density. The falloff in critical current density oneither side of the maximum, or zero compression point, is evident inFIG. 2. This effect was noted to some degree in prior art devices wherethe slight bending of a wire increased the critical current; however,this characteristic was not viewed as a means of increasing the strainlimits.

Wires fabricated in accordance with the present invention receiveessentially the same processing steps as do wires which employ a purelybronze matrix. There is no significant increase in the work-hardeningeffect on the matrix and no additional annealing steps are incurredbecause of the addition of the beryllium.

In a typical fabrication process, a rod of bronze containing 0.1 percentberyllium and from 11 to 14 percent tin by weight is machined to producea longitudinal cavity designed to accept a rod of niobium. The niobiummay be essentially pure or alloyed with a small percentage of otherelements. The niobium rod is inserted in the cavity to form a compositebar which is repeatedly passed through dies to reduce the diameter ofthe bar to that of a wire. Alternatively, the wire may be formed by anextrusion process. Equivalent wire forming processes will be referred togenerally as drawing processes. As required, during the drawing process,the wire is annealed at 300 to 450 degrees centigrade for a period ofapproximately 5 to 25 minutes, depending on the particular annealingtemperature chosen. In the final step, the wire temperature is elevatedto 725° centigrade for a period of hours, depending on the desiredthickness of the niobium-tin film. A six hour period at 725° produced a1.5 micron thick film.

Vanadium-gallium is similar to niobium-tin in that compression andtension reduce the critical current density and a vanadium-gallium wiremay be fabricated in the same manner as the niobium-tin wire describedabove with the exception that the matrix contains 16 to 19 weightpercent of gallium in place of tin and a vanadium rod is substituted forthe niobium rod.

Although a circular cross section has been chosen for exemplary purposesherein, other forms of conductors employing the same principles areconsidered as being within the scope of the invention. For example, anequivalent form is a beryllium strengthened ribbon matrix on which thesuperconducting layer is bonded. Other obvious configurations arepossible without departing from the scope of the invention. Havingdescribed our invention we set forth our claims below.

We claim:
 1. A superconductor wire having improved resistance to loss ofcurrent-carrying capacity when subjected to strain, said superconductorwire comprising at least one filament of a material possessingsuperconducting properties, said filament being encased in a matrixconsisting essentially of up to about 0.2 beryllium and gallium-copperalloy having a coefficient of thermal expansion greater than that ofsaid filament, said matrix containing beryllium in an effectiveconcentration sufficient to induce and maintain said filament undergreater radial and axial compression than that provided by such matrixwithout the beryllium addition, said filament further comprising a filmof vanadium-gallium providing said superconducting properties.
 2. Asuperconductor wire as described in claim 1 in which the gallium contentof said alloy is within the range of 16 to 19 percent by weight.
 3. Asuperconductor wire as described in claim 1 or 2 in which said berylliumis present in said matrix in the range of 0.01 to 0.2 weight percent. 4.A superconducting wire having improved resistance to loss ofcurrent-carrying capacity when subjected to strain, said wire comprisingat least one filament of a material possessing superconductingproperties, said filament comprising a film of vanadium-galliumproviding said superconducting properties and said filament beingencased in a matrix having a coefficient of thermal expansion greaterthan that of said filament, said matrix consisting essentially of copperalloy with 16 to 19 percent by weight of gallium and 0.01 and 0.2percent by weight of beryllium, whereby the tensile strength of saidmatrix is increased sufficiently to induce and maintain said filamentunder greater radial and axial compression than provided by such amatrix without the beryllium addition.